CN103992701A - Method for preparing super hydrophobic polymer composite coating containing nano particles and product thereof - Google Patents
Method for preparing super hydrophobic polymer composite coating containing nano particles and product thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing a super hydrophobic polymer composite coating containing nano particles. The method comprises the following steps: firstly, mixing a coupling agent with a hydrolysis promoter and deionized water to carry out hydrolysis at normal temperature; adding the nano particles, reacting at 50-100 DEG C for 0.25-5 hours under magnetic agitation, so as to obtain modified nano particle powder by post-treatment; sieving the modified nano particle powder, and mixing with a fluorine-containing polymer emulsion; and evenly agitating after diluting by a diluent, coating on a metal substrate, and cooling to room temperature after high-temperature solidification and annealing treatment. The invention proposes a simple method for preparing the super hydrophobic polymer composite coating containing the nano particles. The nano particles are modified by the coupling agent, meanwhile, the adjusting process of pH in the hydrophobic treating process of the nano particles is removed, the modified nano particles are added to the polymer composite coating, and the stable target is achieved by interaction of bonding of a nano particle-coupling agent and a fluorine-containing polymer molecular chain.
Description
Technical field
The present invention relates to the preparation field of high polymer composite coating, be specifically related to preparation method of a kind of super-hydrophobic high polymer composite coating that contains nanoparticle and products thereof.
Background technology
Fluoropolymer is the material that surface can be relatively low, and low friction and high-temperature corrosion resistance performance make it in hydrophobic not sticky field, be widely used.The hydrophobic angle of fluoropolymer intrinsic is 90 °～110 °, compares and still has a certain distance with hydrophobic requirement.Although fluoropolymer is the good material of hydrophobic potential applicability, people are actually rare to the research of fluoropolymer hydrophobic performance so far, major cause be fluoropolymer saturated-CF
2structures shape its unreactiveness, it is carried out to high molecular polymerization modification and also differs and reach surely desirable effect.
Inorganic particulate is the focus of studying at present as additive, and especially, when the diameter of particle is little during to micron, nanoscale, the hydrophobic property that the structure of material microstructure brings has caused scientists interest widely.Inorganic nano-particle becomes the emerging filler of a class as titanium dioxide, silicon-dioxide, aluminum oxide, cupric oxide, cupric sulfide and zinc oxide etc. in the structure of hydrophobic structure.
In the processing mode to nanometer particle-modified, the most general with the modification of coupling agent.By the temperature and time of regulation and control coupling agent treatment, can not only change the size of primary partical, the more important thing is and can make the physico-chemical properties such as reunion, hydrophobicity of nanoparticle change, thereby make nanoparticle more reasonably for people are used.
At present, existing nanoparticle-fluoropolymer super hydrophobic material is actually rare.There is a series of research in the Duan Hui seminar of Wuhan University Of Technology and naval engineering university, in the preparation and ultra-hydrophobicity research > > of < < fluoro-resin/silicon sol compound coating, with tetraethoxy and Union carbide A-162, it is presoma, the tetrafluoroethylene that adulterates in alcohol dissolubility fluororesin solution, has prepared organic and inorganic compound coating by two-step catalysis sol-gel method.In the performance study > > of < < fluorate acrylic acid/SiO 2 hybrid super-hydrophobic coat, tetrafluoroethylene adulterates in the acid alcohol dissolubility fluorinated polymer solution of water shortage, obtain, after complex sol coating, with surface gelation technology, processing and making coatingsurface obtain the hierarchical structure of micro-nano combination.Process is all used salt acid for adjusting pH, and base material is galvanized sheet.
Zheng Yansheng etc. are at < < SiO
2in preparation > > mono-literary composition of/tetrafluoroethylene hydridization super-hydrophobic coat, take sol-gel method and with silane coupling agent to SiO
2sol particles modifying surface with the pH of acetic acid adjusting mixed solution, is applied on the clean sheet glass of surface treatment closing colloidal sol with dip coating in coating preparation process.
Summary of the invention
The present invention is directed to the technical problems such as the complicated process of preparation of adding now nanoparticle hydrophobic material, condition harshness, the method of the super-hydrophobicity high polymer composite coating that a kind of simple preparation contains nanoparticle has been proposed, by nanoparticle is carried out to coupling agent modification, save the regulate process of pH in nanoparticle hydrophobization treating processes simultaneously, nanoparticle after modification is added in polymer composite coating, and the interaction of the Cheng Jianyu fluoropolymer molecule long-chain by nanoparticle-coupling agent reaches stable object.
The preparation method who the invention discloses a kind of super-hydrophobic high polymer composite coating that contains nanoparticle, step is as follows:
(1) coupling agent is mixed and carries out ordinary-temp hydrolysis 1～6h with hydrolytic accelerating agent and deionized water, add nanoparticle, under magnetic agitation, 50～100 ℃ reaction 0.25～5h, through aftertreatment, obtain modified Nano particle powder;
(2) after modified Nano particle powder step (1) being obtained sieves, mix with fluoropolymer emulsion, through thinner dilution, then be coated in substrate after magnetic agitation and ultrasonic dispersion, after hot setting, anneal, be cooled to room temperature.
As preferably, described fluoropolymer emulsion is ptfe emulsion, perfluoroethylene-propylene emulsion, crosses at least one in fluoroalkyl compound emulsion, ethylene tetrafluoroethylene copolymer emulsion, and the viscosity of fluoropolymer emulsion is 800～1000cps.
As preferably, described nanoparticle is at least one in titanium dioxide, silicon-dioxide, aluminum oxide, cupric oxide, cupric sulfide or zinc oxide, and particle diameter is 1～100nm.
As preferably, the mass ratio of described modified Nano particle and fluoropolymer emulsion is 2～60:100; 4～20:100 more preferably.
As preferably, described coupling agent is at least one in aminopropyl triethoxysilane, glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, isopropoxy tricarboxylic acyl titanate, two (dioctylphosphato) metatitanic acid second diester, two (dioctyl pyrophosphoryl oxygen base) hydroxyethanoic acid titanium, two (octyl phenol Soxylat A 25-7) phosphides.
As preferably, described hydrolytic accelerating agent is tetracol phenixin, whiteruss, methyl alcohol, Virahol, propylene glycol, diesel oil or toluene.
Further preferably:
Described coupling agent is aminopropyl triethoxysilane, and hydrolytic accelerating agent is methyl alcohol, and inorganic nano-particle is silicon-dioxide, and particle diameter is 15 ± 5nm;
Or described coupling agent is glycidyl ether oxygen propyl trimethoxy silicane, hydrolytic accelerating agent is Virahol, and inorganic nano-particle is aluminum oxide, and particle diameter is 30nm;
Or described coupling agent is γ-(methacryloxypropyl) propyl trimethoxy silicane, hydrolytic accelerating agent is tetracol phenixin, and inorganic nano-particle is silicon-dioxide, and particle diameter is 15 ± 5nm;
Or described coupling agent is two (dioctylphosphato) metatitanic acid second diester, hydrolytic accelerating agent is propylene glycol, and inorganic nano-particle is titanium dioxide, and particle diameter is 5～10nm;
Or described coupling agent is isopropoxy tricarboxylic acyl titanate, hydrolytic accelerating agent is toluene, and inorganic nano-particle is titanium dioxide, and particle diameter is 5～10nm.
As preferably, the volume ratio of described deionized water, hydrolytic accelerating agent and coupling agent is 20:1～10:0.1～5.
As preferably, described thinner is at least one in DMF, methyl-2-pyrrolidone, acetone, butanone, methyl iso-butyl ketone (MIBK).
As preferably, the described last handling process of step (1) comprises suction filtration, washing, dry and process of lapping.
As preferably, the modified Nano particle powder that step (1) obtains, after the screen filtration of 50 orders (150 μ m), then mixes with fluoropolymer emulsion
As preferably, the described coating method of step (2) is spraying, dip-coating, spin coating or brushing; Described substrate is that surface is through the metal base of sand papering and clean; The temperature of described hot setting is 100 ℃～400 ℃.
The invention also discloses the super-hydrophobicity high polymer composite coating that contains nanoparticle of preparing according to described preparation method.
The present invention is from super-hydrophobic theoretical basis, and the micro-nano structure on building material surface, at 90 °～110 °, is carried out in the hydrophobic angle of the intrinsic of low surface energy fluoropolymer by adding modified Nano particle.Gordian technique of the present invention is the hydrophobically modified to nanoparticle.Compare the method that document has been reported, the advantage of the inventive method is: one, and nanoparticle is directly from market purchasing, by choosing of appropriate particle size nanoparticle, save the loaded down with trivial details preparation process of nanoparticle in ordinary method, and can reach the super-hydrophobic effect of such nano material; Its two, in modifying process, only regulated temperature and reaction times, by choosing suitable hydrolytic accelerating agent, save in the situation that regulates pH and successfully nanoparticle carried out to modification.Method is simple, with low cost, has potential commercial value.
Accompanying drawing explanation
Fig. 1 is the static contact angle test pattern of the super-hydrophobic high polymer composite coating of embodiment 2 preparations;
Fig. 2 is the SEM figure of the super-hydrophobic high polymer composite coating of embodiment 2 preparations, and magnification is 10000 times;
Fig. 3 is the SEM figure of the super-hydrophobic high polymer composite coating of embodiment 2 preparations, and magnification is 50000 times;
Fig. 4 is the SEM figure of the super-hydrophobic high polymer composite coating of embodiment 2 preparations, and magnification is 100000 times.
Embodiment
With embodiment, further set forth the present invention below, in order that better understand the present invention.
Embodiment 1
(1) modifying super hydrophobicity of nanoparticle
5mL aminopropyl triethoxysilane (Nanjing Pin Ning coupling agent company limited, KH-550) ordinary-temp hydrolysis 2h in 10mL methyl alcohol and 100mL deionized water, in the water-bath that magnetic agitation is lower 90 ℃, add silicon-dioxide (particle diameter is 15 ± 5nm, Aladdin reagent company limited) 6g modified-reaction 1h.Be cooled to room temperature suction filtration, washing, 130 ℃ of dried overnight are also ground and are obtained modified particle powder gently.Powder is crossed after 100 order stainless steel meshs, get 0.12g add 3.00g perfluoroethylene-propylene emulsion (Shanghai Pu Chun Industrial Co., Ltd., FEPD121) in, use 0.5g N, dinethylformamide is diluted to after suitable concentration, and successively magnetic agitation 30min and ultrasonic dispersion 20min obtain coating.
(2) coating is in the coating of metal material surface with solidify
Coating is coated on the sand for surface paper polishing iron and steel that also clean is crossed, and is heated to 350 ℃ of after annealings and is cooled to room temperature.
Embodiment 2
(1) modifying super hydrophobicity of nanoparticle
5mL glycidyl ether oxygen propyl trimethoxy silicane (Nanjing Pin Ning coupling agent company limited, KH-560) ordinary-temp hydrolysis 3h in 10mL Virahol and 100mL deionized water, in the water-bath that magnetic agitation is lower 70 ℃, add aluminum oxide (30nm, Aladdin reagent company limited) 6g modified-reaction 2h.Be cooled to room temperature suction filtration, washing, 130 ℃ of dried overnight are also ground and are obtained modified particle powder gently.Powder is crossed after 100 order stainless steel meshs, get 0.24g and add 3.00g ptfe emulsion (Guangdong Li Kalong Science and Technology Ltd., viscosity is 750～800cst) in, with 0.5g methyl-2-pyrrolidone, be diluted to after suitable concentration, successively magnetic agitation 30min and ultrasonic dispersion 20min obtain coating.
(2) coating is in the coating of metal material surface with solidify
Coating is coated on the sand for surface paper polishing aluminium that also clean is crossed, and is heated to 350 ℃ of after annealings and is cooled to room temperature.
Fig. 1 is the static contact angle survey sheet of the super-hydrophobicity high polymer composite coating prepared of the present embodiment, and through contact angle measurement, recording its static contact angle is 149.1 °.
Embodiment 3
(1) modifying super hydrophobicity of nanoparticle
5mL γ-(methacryloxypropyl) propyl trimethoxy silicane (Nanjing Pin Ning coupling agent company limited, KH-570) ordinary-temp hydrolysis 4h in 10mL tetracol phenixin and 100mL deionized water, in the water-bath that magnetic agitation is lower 80 ℃, add silicon-dioxide (particle diameter is 15 ± 5nm, Aladdin reagent company limited) 6g modified-reaction 3h.Be cooled to room temperature suction filtration, washing, 130 ℃ of dried overnight are also ground and are obtained modified particle powder gently.Powder is crossed after 100 order stainless steel meshs, get 0.36g and add 3.00g ethylene tetrafluoroethylene copolymer emulsion (Shanghai Pu Chun Industrial Co., Ltd., F-40), in, by 0.5g acetone diluted, to suitable concentration, successively magnetic agitation 30min and ultrasonic dispersion 20min obtain coating.
(2) coating is in the coating of metal material surface with solidify
Coating is coated on the sand for surface paper polishing copper sheet that also clean is crossed, and is heated to 350 ℃ of after annealings and is cooled to room temperature.
Embodiment 4
(1) modifying super hydrophobicity of nanoparticle
5mL bis-(dioctylphosphato) metatitanic acid second diester (Yangzhou Lida Resin Co., Ltd., LD-212) ordinary-temp hydrolysis 6h in 10mL propylene glycol and 100mL deionized water, in the water-bath that magnetic agitation is lower 50 ℃, add titanium dioxide (particle diameter is 5～10nm, Aladdin reagent company limited) 6g modified-reaction 4h.Be cooled to room temperature suction filtration, washing, 130 ℃ of dried overnight are also ground and are obtained modified particle powder gently.Powder is crossed after 100 order stainless steel meshs, getting 0.48g adds 3.00g to cross fluoroalkyl compound emulsion (Shanghai Pu Chun Industrial Co., Ltd., PFAD335D) in, with 0.5g butanone, be diluted to after suitable concentration, successively magnetic agitation 30min and ultrasonic dispersion 20min obtain coating.
(2) coating is in the coating of metal material surface with solidify
Coating is coated on the sand for surface paper polishing stainless material that also clean is crossed, and is heated to 350 ℃ of after annealings and is cooled to room temperature.
Embodiment 5
(1) modifying super hydrophobicity of nanoparticle
5mL isopropoxy tricarboxylic acyl titanate (Yangzhou Lida Resin Co., Ltd.; LD-101) ordinary-temp hydrolysis 1h in 10mL toluene and 100mL deionized water; in the water-bath that magnetic agitation is lower 60 ℃, add titanium dioxide (particle diameter is 5～10nm, Aladdin reagent company limited) 6g modified-reaction 4h.Be cooled to room temperature suction filtration, washing, 130 ℃ of dried overnight are also ground and are obtained modified particle powder gently.Powder is crossed after 100 order stainless steel meshs, get 0.60g and add 3.00g perfluoroethylene-propylene emulsion (Shanghai Pu Chun Industrial Co., Ltd., FEPD121) in, by 0.5g methyl iso-butyl ketone (MIBK), be diluted to after suitable concentration, successively magnetic agitation 30min and ultrasonic dispersion 20min obtain coating.
(2) coating is in the coating of metal material surface with solidify
Coating is coated on the sand for surface paper polishing iron and steel that also clean is crossed, and is heated to 350 ℃ of after annealings and is cooled to room temperature.
Comparative example 1
(1) interpolation of nanoparticle
By the aluminum oxide (30nm of 0.12g non-modified, Aladdin reagent company limited) cross after 100 order stainless steel meshs, add 3.00g perfluoroethylene-propylene emulsion (Shanghai Pu Chun Industrial Co., Ltd., FEPD121) in, by 0.5g methyl iso-butyl ketone (MIBK), be diluted to after suitable concentration, successively magnetic agitation 30min and ultrasonic dispersion 20min obtain coating.
(2) coating is in the coating of metal material surface with solidify
Coating is coated on the sand for surface paper polishing metallic substance that also clean is crossed, and is heated to 350 ℃ of after annealings and is cooled to room temperature.
Comparative example 2
(1) modifying super hydrophobicity of nanoparticle
5mL aminopropyl triethoxysilane (Nanjing Pin Ning coupling agent company limited, KH-550) ordinary-temp hydrolysis 2h in 10mL methyl alcohol and 100mL deionized water, in the water-bath that magnetic agitation is lower 90 ℃, add silicon-dioxide (particle diameter is 15 ± 5nm, Aladdin reagent company limited) 6g modified-reaction 1h.Be cooled to room temperature suction filtration, washing, 130 ℃ of dried overnight are also ground and are obtained modified particle powder gently.Powder is crossed after 100 order stainless steel meshs, get 0.12g add 3.00g perfluoroethylene-propylene emulsion (Shanghai Pu Chun Industrial Co., Ltd., FEPD121) in, successively magnetic agitation 30min and ultrasonic dispersion 20min obtain coating.
(2) coating is in the coating of metal material surface with solidify
Coating is coated on the sand for surface paper polishing iron and steel that also clean is crossed, and is heated to 350 ℃ of after annealings and is cooled to room temperature.
Performance test
The super-hydrophobic high polymer composite coating that contains nanoparticle to embodiment 1～5 and comparative example 1,2 preparations carries out hydrophobic angle and sticking power and pencil hardness test as described below:
1. pencil hardness test
Testing standard: GB/T6739-2006
Testing method: 1 group of Chinese board advanced drawing pencil for experiment, comprises each of 6H, 5H, 4H, 3H, 2H, H, HB, B, 2B, 3B, 4B, 5B and 6B pencil.By the penknife rod part of pruning, make pen core be the cylindric about 3mm that exposes.On experiment table, place 400# sand paper, vertically hold pencil, keep 90 ° of front and back mobile lead pencils on sand paper with sand paper, pencil-lead tip is polished.Continue mobile lead pencil until obtain a smooth smooth circular cross section, and edge do not have chip and breach (all repeating this step before at every turn using pencil).Hand-held pencil tilts approximately 45 °, with pencil-lead degree of breaking into not, on the material surface of the super-hydrophobicity polymer compound film that contains nanoparticle, towards the direction of leaving experimenter, with uniform about 1cm/s speed, push 1cm left and right, the pencil of same label repeats five roads, all chips of cleaning pencil-lead on coatingsurface with Great Wall board advanced drawing rubber, show so that cut is more apparent.
The situation that coating scratches: Wu road scratches in experiment, if any the two Dao Huo bis-above scratch bottoms in road, film, the pencil of using last position hardness label instead carries out same experiment, until find out to film, is scratched the pencil below two roads, writes down the hardness label of this pencil.
The abrasive situation of coating: Wu road scratches in test, if any two Dao Huo bis-roads, abrading above bottom films, use the pencil of last position hardness label instead and test equally, until find out to film, be scratched pencils more than two Dao Huo bis-roads, write down the hardness label of this pencil.
Coating hardness is judged:
Coating scratches: for mutual contiguous two pencils of hardness label, finding out films is scratched after two roads or above and pencil less than two roads, using the pencil hardness less than two roads as the pencil hardness of filming.
Coating scratch: for mutual two the contiguous pencils of hardness label, find out coating and be scratched after two roads or above and the pencil less than two roads, the pencil hardness using the pencil hardness less than two roads as coating.
2. sticking power test
Testing standard: GB/T9286-1998
Testing method: the material that is coated with the super-hydrophobicity high polymer composite coating of nanoparticle is placed on experiment table, hand-held stroke of lattice device handle, make multi-edge cutting knife perpendicular to material plane, with the gimmick of not trembleing of uniform pressure, balance and the speed of 20mm/s～50mm/s, cut and draw.By material half-twist, cutting the salty multiple above operation of cutting-up with formation lattice battle array.With banister brush along lattice battle array diagonal lines lightly backward, brush applied coating 5 times forward.Experiment completes at three different positionss of coating.By wide, for the senior scotch tape of 3M600 of 19mm is attached on whole stroke of lattice, with minimum angles, tear, check the shared per-cent of quantity that coatingsurface has been sticked by adhesive tape.
Grade classification:
ISO grade: 0 grade
Cut edge is completely smooth, and none lattice comes off.
ISO grade: 1 grade
In the intersection of otch, there is a little disbonding, but cross cut area is influenced, can not obviously be greater than 5%.
ISO grade: 2 grades
At otch infall and/or have coating shedding along notching edge, affected cross cut area is obviously greater than 5%, but can not obviously be greater than 15%.
ISO grade: 3 grades
Coating partly or entirely comes off with large fragment along cut edge, and/or partly or entirely peels off on grid different sites, and affected cross cut area is obviously greater than 15%, but can not obviously be greater than 35%.
ISO grade: 4 grades
Along cut edge, large fragment peels off coating, and/or some grids part or all occur coming off, and affected cross cut area is obviously greater than 35%, but can not obviously be greater than 65%.
ISO grade: 5 grades
The degree of peeling off is over 4 grades.
Table 1
Hydrophobic angle, pencil hardness and the sticking power test result of the super-hydrophobicity high polymer composite coating that contains nanoparticle that table 1 is prepared respectively for embodiment 1～5 and comparative example 1,2.
As can be seen from Table 1, the static contact angle of the super-hydrophobicity high polymer composite coating that contains nanoparticle prepared by the present invention is all more than 135 °, and sticking power and pencil hardness are all in good rank.And the result of comparative example 1 shows, although unmodified nanoparticle adds the coating obtaining after dispersion in fluoropolymer emulsion also to have super-hydrophobic effect, surface is very coarse, and adhesion property is very poor, there is no practical value.Contrast nanometer particle-modified front and back and cross the status discovery of screen cloth, non-modified nanoparticle tends to assemble and is not easy by sieve aperture, and the particle after modification is compared and more easily passed through, and from this point, the successful modification of coupling agent to nanoparticle has also been described.The coating of comparative example 2 is than the homogeneity on embodiment 1 surface also non-constant, and having embodied thinner of the present invention has considerable influence to the nanoparticle degree of being uniformly dispersed.
Above embodiment only preferably gives an example for the present invention, does not limit the scope of the invention, and allly in principle of the present invention, does any modification, replacement and improvement, is all interpreted as still within protection scope of the present invention.
Claims (10)
1. a preparation method who contains the super-hydrophobic high polymer composite coating of nanoparticle, is characterized in that, step is as follows:
(1) coupling agent is mixed and carries out ordinary-temp hydrolysis 1～6h with hydrolytic accelerating agent and deionized water, add nanoparticle, under magnetic agitation, 50～100 ℃ reaction 0.25～5h, through aftertreatment, obtain modified Nano particle powder;
(2) after modified Nano particle powder step (1) being obtained sieves, mix with fluoropolymer emulsion, through thinner dilution, then be coated in substrate after magnetic agitation and ultrasonic dispersion, after hot setting, anneal, be cooled to room temperature.
2. preparation method according to claim 1, it is characterized in that, described fluoropolymer emulsion is at least one in ptfe emulsion, perfluoroethylene-propylene emulsion, mistake fluoroalkyl compound emulsion, ethylene tetrafluoroethylene copolymer emulsion, and the viscosity of fluoropolymer emulsion is 800～1000cps.
3. preparation method according to claim 1, is characterized in that, described nanoparticle is at least one in titanium dioxide, silicon-dioxide, aluminum oxide, cupric oxide, cupric sulfide or zinc oxide, and particle diameter is 1～100nm.
4. according to the preparation method described in claim 1 or 2 or 3, it is characterized in that, the mass ratio of described modified Nano particle and fluoropolymer emulsion is 2～60:100.
5. its preparation method according to claim 1; it is characterized in that, described coupling agent is at least one in aminopropyl triethoxysilane, glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, isopropoxy tricarboxylic acyl titanate, two (dioctylphosphato) metatitanic acid second diester, two (dioctyl pyrophosphoryl oxygen base) hydroxyethanoic acid titanium, two (octyl phenol Soxylat A 25-7) phosphides.
6. its preparation method according to claim 1, is characterized in that, described hydrolytic accelerating agent is tetracol phenixin, whiteruss, methyl alcohol, Virahol, propylene glycol, diesel oil or toluene.
7. preparation method according to claim 1, is characterized in that, the volume ratio of described deionized water, hydrolytic accelerating agent and coupling agent is 20:1～10:0.1～5.
8. preparation method according to claim 1, is characterized in that, described thinner is at least one in DMF, methyl-2-pyrrolidone, acetone, butanone, methyl iso-butyl ketone (MIBK).
9. preparation method according to claim 1, is characterized in that, described coating method is spraying, dip-coating, spin coating or brushing; Described substrate is that surface is through the metal base of sand papering and clean; The temperature of described hot setting is 100 ℃～400 ℃.
10. a super-hydrophobic high polymer composite coating that contains nanoparticle of preparing according to the preparation method described in the arbitrary claim of claim 1～9.
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